Ilmenite beneficiation with fecl&#39; 3 &#39;glaeser; hans hellmut

ABSTRACT

A process for the selective chlorination of the iron constituent of titaniferous ores using FeCl3 as the chlorinating agent, and using a reductant selected from at least one of the group consisting of a solid carbonaceous material and carbon monoxide. The FeCl3 can be produced by oxidizing the FeCl2 resulting from the selective chlorination, thereby providing for a recycle operation.

United States Patent 1191 Glaeser Dec. 16, 1975 ILMENITE BENEFICIATION WITH FeCl 2,480,184 8/1949 Erasmus 423/149 [751 Inventor: Hans Helm Glaser, Wilmington, 21322132; 211322 32222222222111: :jjiiijjjiiiiiii1 9212 Del. 2,762,700 9/1956 Brooks 75/34 [73] Assignee: E. I. Du Pont de Nemours & C0., 3:322 5 :22:

w'lmmgton 31699206 10 1972 Dunn 75/1 [22] Filed: Apr. 19, 1974 [21] Appl. NO 462,535 Primary Examiner- Peter D. Rosenberg [52] US. Cl. 75/1; 75/34; 423/149 [57] ABSTRACT 51 lm. c1. .1 C211; 1/00;C01G 49/02 A 9 for h 9 chlormfitlon of [58] Field of Search 75/1 'r, 34, 104, 112; Consumer of "tamferous P Fecla as 4237149, 493 chlorinating agent, and usmg a reductant selected from at least one of the group consisting of a solid car- [56] References Cited bonaceous material and carbon monoxide. The FeCl UNITED STATES PATENTS can be produced by oxidizing the FeCl resulting from the selective chlorination, thereby providing for a re- 1,917,789 7/1933 Bacon 423/149 Cycle Operation 1,994,367 3/1935 Millar 423/149 2,184,885 12/1939 Muskat 75/1 14 Claims, 4 Drawing Figures US. Patent Dec. 16, 1975 Sheet20f4 3,926,614

FIG. 2

US. Patent Dec. 16, 1975 Sheet3of4 3,926,614

CO or (IO/CO O2 or Clz FIG. 3

US. Patent Dec. 16, 1975 Sheet40f4 3,926,614

ILMENITE BENEFICIATION WITH FeCl BACKGROUND OF THE INVENTION For many years, a great deal of attention has been devoted to techniques aimed at the effective separation of the titanium and iron constituents of titaniferous ores such as ilmenite. Nonselective chlorination techniques, i.e., in which the two metals are chlorinated simultaneously and the chlorides then separated from one another, have proven to be sufficiently effective that they are now practiced in the manufacture of titanium dioxide (TiO pigments, particularly by the so-called chloride process involving the oxidation of titanium tetrachloride (TiCl Such techniques are much less efficient than would be desired, however, since depending upon the iron content of the ore a considerable amount of costly chlorinating agent, conventionally consisting primarily of chlorine, may be consumed in producing iron chlorides as by-products, which by-products have little commercial value.

Other techniques for separating the iron and titanium constituents of ores have been devised that involve selectively chlorinating the iron content, thereby leaving an upgraded or beneficiated TiO fraction. A typical technique for beneficiation is described in Muskat et al. US. Pat. No. 2,184,884. According thereto an ore such as ilmenite is mixed with l to 12% by weight of carbon (based on total weight of the ore), heated to at least 500C. and exposed to a chlorinating agent. The chlorinating agent employed in the experimental examples of Muskat et al. is gaseous chlorine, although the disclosure contemplates the use of other chlorinating agents such as hydrogen chloride and phosgene in conjunction with chlorine. Such beneficiation techniques have achieved some measure of commercial importance, but they have not served to lessen the problems associated with the formation of iron chloride by-products and the attendant consumption of chlorine.

One approach to solvingthe Waste disposal problem might be to convert the. iron chlorides to metallic iron or some form of iron oxide thereby recovering the chlorine content as gaseous chlorine, but such conversion is difficult to achieve in an economic fashion.

In the specification set forth hereinafter I describe my findings of a cyclic process for separating the titanium and iron constituents of titaniferous ore by selectively chlorinating the iron constituent utilizing ferric chloride (FeCl This ferric chloride (FeCl is generated in the amount needed to satisfy the requirement of the process by oxidation of the ferrous chloride (Fecl produced by chlorination of the iron constituent of the ore.

SUMMARY or THE INVENTION In accordance with my invention, there is provided a cyclic chlorination/oxidation process for the separation of titanium and iron constituents of titaniferous materials in such a way that the iron constituent is chlorinated but there is not appreciable net yield of titanium chloride from the titanium constituent. The chlorination is carried out in the presence of a solid carbonaceous material or gaseous carbon monoxide or mixtures thereof as a reductant. When the reductant consists essentially of a solid carbonaceous material, it is utilized in an amount such that the total carbon contentthereof is at least equal to the stoichiometric amount to produce carbon dioxide, based on the oxygen bound to the iron constituent of the titaniferous material, and less than or about equal to the stoichiometric amount to produce carbon monoxide, based on said oxygen. When the reductant contains gaseous carbon monoxide, it is fed in an amount greater than required to convert the balance of said oxygen to carbon dioxide. It follows that when essentially no solid carbonaceous material is present in the reductant gaseous carbon monoxide is fed in an amount greater than the stoichiometric amount to produce carbon dioxide based on said oxygen. The selective chlorination utilizes FeCl as the chlorinating agent preferably in an amount which is about stoichiometric for the iron constituent of the titaniferous material.

The temperature maintained during the chlorination depends on the dew point of the FeCl produced thereby and should be sufficiently high to avoid the accumulation of liquid FeCl In the practice of this invention an elevated temperature of at least 950C. is maintained during the chlorination. The upper temperature at which the chlorination can take place is limited primarily by energy economics and the materials of construction of the vessel in which the chlorination is conducted. A currently practical limit is about 1,300C. Preferably the temperature maintained during chlorination will be from l,OOOC. to l,lO0C.

It is a significant feature of this invention that the FeCl utilized as the chlorinating agent, can be obtained by oxidizing the FeCl which is the iron chloride produced by the selective chlorination of this invention, with a gaseous mixture containing oxygen. In this way the FeCl can be recycled, after oxidation to Fe O and FeCl and removal of re o The process of this invention can also be practiced using FeCl which is obtained directly, as a waste product, from the conventional chloride process, thereby enabling the process of this invention to be operated in combination with the conventional chloride process.

DETAILED DESCRIPTION OF THE INVENTION In connection with the detailsof the invention hereinafter described it is noted there will be used the formula FeTiO which is an idealized formula chosen to represent the titaniferous materials of interest. The empirical formula will vary, as is known, from one ore source to another. In this respect the term ore will be 'used herein in a general way since, while it is not essen- 'tialthat the titaniferous material be an ore, normally it will at least be drived from an ore source. The formula FeCl is used throughout this specification for convenience to designate ferric chloride both as such and as 1 to provide a high quality beneficiate. It is to be understood that conversion of at least about by weight of the iron in the ore is intended by the expression essentially completely when used in this connection throughout the specification. Ores from which at least by weight of the iron in the ore has been separated are decidedly preferred and can normally be produced without difficulty by the process of this invention.

It is also noted that when reference is made herein to the selective chlorination of the iron constituent of the ore, this is not intended to be construed as necessarily precluding the net chlorination of minor quantities of other metals in the ore. Under certain conditions, the

product of the selective chlorination reaction, which is FeCl or the major chlorinating agent FeCl can themselves chlorinate some of the titanium in the ore. Of course, any net yield of titanium chloride is a condition which is to be avoided as much as possible since it is desired that as much titanium as possible remain in the beneficiated ore. A judicious selection of the process conditions in accordance with the disclosure herein makes it readily possible to operate such that the net yield of titanium chloride does not exceed about by weight of the titanium in the titaniferous ore, hence the expression no appreciable net yield of titanium chloride is employed herein. Most often, as is preferred, the percentage will be 5% or less, an amount which for all practical purposes can be ignored.

Thc'process of the invention can be expressed according to the following reaction (as in the case of all reactions in the specification, it will be referred to by Roman numeral designation):

(l) 4FeTiO 4C( or C0) 2- 4TiO 2Fe O 4CO(or CO (II) I 4FeTiO 4C(or C0) 8FeCl l2FeCl 4CO(or CO (III) l2FeCl 30 21 620;; 8FeCl 4TiO Since the titanium present in the ore does not significantly enter the reaction, it will be understood that ores containing varying ratios of titanium to iron can be used and equations (I) to (III) would be modified to represent the composition of the actual reactants.

The preferred technique for effecting Reaction (II) in accordance 'with the process of this invention involves the use of FeCl in the vapor phase. The FeCl is preferably produced by the oxidation of the FeCl of Reaction (II) with a gaseous mixture containing oxygen in an amount at least 20 percent by volume, e.g., air, according to Reaction (III). The FeCl utilized in Reaction (II) can also be generated by direct chlorination of the FeCl with gaseous chlorine, however, this route is not particularly economically advantageous since chlorine is a relatively expensive reactant. The FeCl can be vaporized directly by heating solid FeCl obtained from any source. The FeCl vapors are then brought into contact with a mixture of ore and reductant, e.g., carbon or carbon monoxide, in a reactor. The FeCl which forms during Reaction (II) approximates the amount of FeCl that is consumed during Reaction (III). The FeCl formed during Reaction (II) can be removed, for example, by the aid of an inert gas purge, and condensed. If desired, the ore/reductant mixture can first be heated to a temperature of 500C. or more out of contact with the FeCl to initiate some prereduction, primarily of the iron content.

Furthermore, it has been discovered that ratios of [CO ]/[CO] in excess of 0.01 provide for essentially complete conversion of iron with no appreciable net yield of titanium chloride. Since beneficiation increases with increasing [COfl/[CO] ratio, it is desirable to maintain a substantial CO partial pressure. High CO 4 partial pressure can be achieved by a variety of methods which areknown to persons skilled in the art.

The FeCl that forms as a product in equation (II) can undergo an equilibrium reaction with TiO and carbon to yield TiCl and Fe at temperatures above 950C. according to the following equation:

(IV) TiO 2C 2FeCl 1; TiCl 2Fe 2C0.

The stoichiometry of the equation shows that excess carbon not consumed in the reduction of iron oxide would result in the formation of TiCl while increasing the amount of CO, or the partial pressure of CO, tends to supress the reaction. The presence of CO contributes significantly to supressing Reaction (IV) because CO reacts with carbon thereby increasing the CO partial pressure.

Therefore, when using FeCl as the chlorinating agent, it is advantageous to utilize the least possible amount of carbon, i.e., about equal to or less than stoichiometric with respect to the oxygen bound to the iron constituent of the ore.

DESCRIPTION OF THE DRAWINGS The invention will be further illustrated with reference to the Drawings.

FIG. 1 illustrates on a calculated basis the effect of the value of the [CO ]/[CO] ratio on the selectivity of the reduction/chlorination process of the invention. FIGS. 2, 3 and 4 illustrate various forms of laboratory apparatus, shown schematically and not to scale, that maybe used for carrying out the process of the invention.

Referring to FIG. I, the ratio of [CO ]/[CO] is varied from 0.001 upward by varying the amount of carbon added to FeTiO when reacting with FeCl at l,050C. Substantially the same dependence of the chlorination selectivity on the [COfl/[CO] ratio is found at temperatures as high as l,500C.

Referring to FIG. 2, there is employed a simple type of fixed bed reactor constituting elongated silica tube 1 in which an iron chloride charge, i.e., FeCl and an orel-carbon mixture is placed. These may be maintained in their respective positions by means of silica wool 2 or similar porous material. A stream of inert gas such .as argon, helium or the like enters through line 3 to serve as a purge in the system to aid in withdrawing and collecting FeCl produced. Exit gases are carried out through line 4. A stationary heater or furnace 5, shown partially cutaway, is adapted to receive and enclose the elongated silica tube 1. The heater, which may be, for example, an electric heater of several sections, will typically be equipped with a thermocouple or other device not shown, to measure and record a predetermined temperature to be applied to the charges. In operation the charges are placed in the tube as shown, the flow of purge gas is commenced and the tube is inserted sufficiently into the heater that the ore/carbon blend is first brought to temperature. At temperatures below 950C., some reduction of the ore may commence. The tube is then further inserted into the furnace so that the iron chloride charge is caused to vaporize. Slow continual insertion of the tube into the furnace, i.e., left to right in the drawing, results in a stream of FeCl;, vapor being generated and passed into contact with the ore/-carbon mixture. Some iron chloride and/or other materials may be found to be condensed on the walls of tube 1, but in any event, an exit gas results which is composed of inert gas, FeCl unreacted FeCl and possibly some titanium chloride. The exit gas, and more importantly the FeCl constituent can be collected by any suitable means, not shown. A simple ice bath condenser arrangement may be employed for this purpose.

FIG. 3 shows a vertical silica reactor that can be used to react a fixed bed of ore or ore and carbon in a steady stream of FeCl In this case a vertical silica reactor shown generally as 6 is composed of upper sections 7 and 8 and a lower section 9 positioned within a furnace composed of sections 10 and 11. A stream of CO or a mixture of CO and CO in a predetermined amount enters the reactor through tube 12 and passes outwardly through perforations 13 in the wall of tube 14 and through silica wool 15, then passes into contact with a heated ore or ore/carbon blend in the lower section 9 of the reactor. The heated FeCl which is held in place by support 16, in upper section 7 of the reactor is reacted with a predetermined amount of 0 or Cl which enters the reactor through tube 17. The FeCl vapor thus formed passes through support 16 and through silica wool 15, which is held in place by support 18, and passes into contact with ore or ore/carbon blend in the lower section 9 of the reactor. The FeCl exit gases, and any minor amounts of TiCl and unreacted FeCl formed from the chlorination reaction pass through silica frit 19. The FeCl is condensed in receptacle 20 while any TiCl formed passes through tube 21 with exiting gases and can be condensed in an ice/salt bath or any other conventional manner.

FIG. 4 shows a vertical silica reactor that can be used to react a fluidized bed of ore and carbon in a steady stream of FeCl The reactor, shown generally as 22, is composed of upper section 23, positioned within a fur nace composed of sections 24 and 25, and a lower section 26, positioned within ceramic heater 27. In the lower portion of the reactor 26 a bed of solid FeCl is contacted with a metered quantity of 0 gas entering through line 28. The two react and the resultant FeCl vapors then pass upwardly into contact with the ore/- carbon mixture. The ore/-carbon mixture is also contacted with a gaseous mixture containing inert gas and carbon monoxide entering through line 29. The FeCl resulting from the selective chlorination of the ore passes through line 30 and is collected in receptacle 31.

Also in FIG. 4, inert gas can be introduced at line 32. The ore/carbon mixture is held in place by coarse silica frit 33. Silica wool pads 34 are used as shown to maintain materials in place in reactor 22 and to assist in preventing the passage of blowover particles from the bed.

In operation of the device of FIG. 4, ore and carbon in the desired particle size and proportions are mixed and placed in upper reactor section 23. The lower section 26 is filled with a column of crushed FeCl Moisture and FeCl traces can be removed from'the reactor by applying heat but below the boiling point of FeCl while an argon purge is maintained through line 28. Then the temperature of the upper section 23 is raised, e.g., to 950C. or above, to commence prereduction of the ore, while passing a stream of inert gas through line 29. This heating may be continued for an hour or more to effect reduction. Oxidation of the FeCl is then commenced by metering 0 at the desired rate into the FeCl bed through line 28. Argon may be passed into the system at 32 to prevent pluggage. While the FeCl so produced passes into contact with the ore/carbon mixture, a mixture of argon and carbon monoxide is metered at the desired rate through line 29. The FeCl produced by the selective chlorination of the iron constituent of the ore passes through upper silica wool pads 34 and is carried by the argon stream through line 30 to receptacle 31 where it is condensed. The reacted bed is removed for reactor 22, washed with water and analyzed for iron and titanium. The reacted bed of FeCl consisting primarily of IFe O is removed from reactor lower section 26 and can be replaced with the FeCl collected in 31.

DETAILED PROCESS DESCRIPTION The titaniferous materials employed in the practice of the invention may be iron/titanium oxide ores obtained from a wide variety of sources or they may be other iron oxide and titanium oxide containing materials. It will be apparent that since the process of the invention involves the selective chlorination of the iron constituent, i.e., beneficiation, low grade ores containing relatively high amounts of iron can readily be treated.

For convenience, the formula FeTiO has been used herein to describe the titaniferous materials of interest for practice of the invention. This is the formula typically ascribed to true ilmenite ores, which contain about equimolar amounts of iron and titanium. ln practice, any titaniferous material may be utilized provided it contains sufficient titanium to make its recovery economically attractive. Materials containing at least 10 percent, and preferably at least 20%, by weight of titanium are thus best employed. The amount of iron in the material will also usually be at least 10 percent, typically at least 20 percent, by weight but there is no practical reason why ores containing much less iron cannot be processed. The oxidic titaniferous ores referred to generally as ilmenite ores and containing about 20 to 50% titanium and 10 to 50% iron represent a preferred titaniferous material for use in the invention because they are widely available at a relatively low cost such that the recovery of the titanium can be most economically performed. It is to be understood, however, that the various types of ilmenite ores, rutile ores, slags and residues, including mixtures of any such materials, may also be effectively treated in accordance with the invention.

It will be understood that the actual reactions which occur in the course of the beneficiation process of the invention can be highly complex ones depending upon the chemical composition of the titaniferous material employed. In this respect the reactions set forth in this specification are intended to be representative of the primary chemical changes which occur and should not be interpreted as excluding the possibility that secondary or side reactions may" also occur.

In general it is desired that the titaniferous material be in a particulate or at least porous form so that sufficient surface area is accessible for the reduction and selective chlorination reactions to take place at reasonable rates. Sand ores and the like, because of their small particle size, can typically be used as such without further size reduction. Some form of grinding step is generally necessary with massive ores, however, in which case the extent and cost of grinding will have to be balanced against the extent to which the reaction rate will be benefited. Particles on the order of 1 mm or less are generally the most useful. For convenience, a particulate material can be formed into briquettes, e.g., with carbon and binders if necessary.

The solid carbonaceous material employed in the practice of the invention may be carbon as such, e.g., charcoal, coal, or coke, or it may be any other material which on heating will produce carbon or carbon compounds in a form suitable as are reducing agent. Materials composed essentially of carbon are preferred in order to reduce or eliminate any side reactions. Preferably, the solid carbonaceous material will also be used in particulate or at least porous form in order to provide a high degree of surface area. However, depending upon the apparatus employed, powders or other excessively small size particles of carbon, i.e., those below 50 u, may tend to result in an excessively high blowover from the reactor. For this reason somewhat larger particles of carbon, i.e., of 0.1 to mm, are the most useful, especially when the particles are of a porous character.

The total amount of chlorinating agent, i.e., FeCl employed in carrying out a manufacturing process of the invention should, of course, be sufficient to permit chlorination of essentially all of the iron content of the ore. Where only FeCl is produced this would mean about two FeCl molecules per iron atom.

For reasons of efficiency it is desirable, if not necessary, to insure that during the beneficiation process moisture and other materials that might consume a portion of the FeCl are not present in the reactor.

The process of the invention can be carried out using a wide variety of reactors either on a batch basis or a continuous basis. Fluid bed operations are advantageous for continuous operation.

Depending upon the type of apparatus employed, and the way that the various reactants are supplied and intermixed, the requisite proportions of ore, carbon and FeCl specified herein need not necessarily be maintained throughout the duration of the reaction. For example, procedures can be devised for intermittent addition of one or more materials and/or for the withdrawal and recycling of one or more materials.

The process of the invention will be exemplified by procedures operating at atmospheric pressure, or slightly thereabove. Subatmospheric or superatmospheric pressure can be used, however. It is to be noted that regardless of the nature of the apparatus employed, difficulty can be experienced in collecting as such the entire quantity of FeCl generated in the process. This is particularly true for laboratory or other small scale operations as the usual condensation techniques tend to allow some FeCl to be lost, either to the atmosphere or by reaction with moisture. For this reason, it is frequently more accurate to ascertain the percent iron chlorinated from the quantity of iron which remains as a residue. The examples hereinafter indicate conversions which have been determined in this way. The practice may, on the one hand, involve igniting the residue of the ore/carbon mixture to burn off carbon followed by chemical analysis for iron and titanium. These would then be compared with the original ore analysis. Alternatively, the residue may be subjected to magnetic separation to remove carbon and other nonmagnetic materials from the iron/titanium portion followed by analysis of the fractions.

The invention is further illustrated by the following examples in which parts and percentages are by weight unless otherwise specified. The TiO and total Fe values reported for ore analyses should be considered accurate within about one percentage point owing to vari- 8 ations fro,m,one sample to another. Mesh sizes therein refer to,U.S. Standard Sieve sizes. Gas flow rates are measured at room temperature. 7

EXAMPLE 1 A 50.0 g sample of a titaniferous sand ore (analyzing 64.6% TiO 22.3% total Fe, 21.5% Fe, and containing minor amounts of SiO and other oxides) of mesh size 60+l60 is blended with 3.5 g of dried particulate carbon and placed in an elongated silica tube (of 42 mm inside diameter) shown in FIG. 2. The blend, which fills the cross section of the tube, is held in place with silica wool.

The carbon is a standard laboratory grade charcoal (sold by Fisher Scientific Company, Fair Lawn, N.J., U.S.A., under the trademark Darco G-60 activated carbon). It is characterized by a particle diameter of much less than 400 mesh and a surface area of about 650 m /g.

Then 232 g of a commercially available reagent grade anhydrous FeCl is placed in the tube and heated in portions to 1,050C. For 120 minutes the vaporized FeCl is carried into the reactor by a stream of argon flowing at a rate of about 200 cc/min. FeCl traces of TiCl, and unreacted FeCl are collected by cooling and condensation. At the end of the run the argon stream is used to free the residual ore/carbon bed of gaseous chlorides.

The residual ore/carbon bed, weighing 31.9 g, is separated magnetically into two fractions. The magnetic fraction, weighing 1.0 g, is analyzed and found to contain 80.0% TiO and 13.2% Fe. The nonmagnetic fraction is ignited in air at about 900C, leaving a beneficiate that weighs 30.3 g and analyzes 94.5% TiO and 3.6% Fe O On the basis of the original iron and titanium contents of the ore and the relative proportions of each in both fractions of the bed it is determined that the beneficiate retains 91.1% of the Ti and 8.0% of the Fe in the unreacted ore.

EXAMPLE 2 The apparatus is of the type shown in FIG. 3. In the lower section of the reactor is placed 100 g of the titaniferous sand ore described in Example 1, blended with 7.1 g of petroleum coke of mesh size 80+120 containing about 2% sulfur as the major impurity. An excess of a commercially available, typically 99.5 percent pure, solid particulate FeCl is placed in the upper section of the reactor.

The ore/carbon blend is heated to 1,050C. in a stream of argon flowing at a rate of about 100 cc/min and then contacted with a stream of CO flowing at a rate of about 238 cc/min for 15 minutes. While continuing the flow of CO, the blend is contacted with FeCl The FeCl is generated from FeCl which is preheated to 500C. and contacted with a stream of C1 flowing at a rate of 0.301 g/min over a period of minutes, thus providing 138 g of total FeCl The CO stream provides a total of 31.6 g CO during reduction and chlorination.

After completion of the reaction, the flow of argon is resumed for 60 minutes. The reactor is then cooled, after which the residual bed is removed, ignited in air at 900C, and analyzed. A beneficiate is obtained which weighs 64.6 g and is found to contain 95.3% TiO and 3.0% Fe O On the basis of the original iron and titanium contents of the ore and the relative proportions of i each in the beneficiate, it is determined that the benefi- 9 ciate retains 95.3% of the Ti and 6.1% of the iron in the unreacted ore.

EXAMPLE 3 The procedure of Example 2 is followed except that the titaniferous sand ore is not blended with any solid carbon and the CO is replaced by an equal volume of a mixture of CO and CO containing about 1 percent by volume of CO The beneficiate removed from the reactor weighs 63.9 g and analyzes 95.9% TiO and 1.8% Fe O It is determined that the beneficiate retains 94.9% of the Ti and 3.6% of the Fe in the unreacted ore.

EXAMPLE 4 CO flows at a rate of 60 cc/min for minutes prior to the chlorination and during the chlorination. A stream of O flowing at a rate of 55 cc/min and providing a total of 11.2 g 0 contacts the FeCl at 500C. for a total of 156 minutes. This gives a feed of about 152 g FeCl to the reaction chamber.

After cooling the reactor, the residual bed is removed, ignited in air at 900C. and analyzed. The beneficiate weighs 63.9 g and analyzes 96.0% TiO and 2.1% Fe O FeCl which condenses in receptacle of FIG. 3 is collected as a starting material for a subsequent run.

The above procedure is repeated and the resulting beneficiate weighs 65.9 g and analyzes 92.1% TiO and 3.5% Fe O Chlorination with FeCl from recycle FeCl The above procedure is repeated using :recycle FeCl obtained from the previous runs. Before its use, the

FeCl is heated under argon above the melting point to remove traces of FeCl;, and moisture. It is then allowed to solidify and is crushed with a mortar and pestle.

The resulting beneficiate weighs 64.8 g and analyzes 96.8% TiO and 1.6% F6 0 It is determined that the beneficiate retains 97.0% of the Ti and 3.2% of the Fe in the unreacted ore. 1.9 g TiCL, is also collected.

The reacted bed of FeCl in the upper section of the reactor is found to contain unreacted FeCl and byproduct Fe O The Fe O is freed from unreacted FeCl by water-leaching, is dried by heating in air, and is analyzed. It contains an amount of iron equivalent to 98.5% of the amount of iron in the unreacted ore. The weight of FeCl condensing in the receptacle of FIG. 3 equals 87.5% of the weight of FeCl consumed by oxidation in the upper section of the reactor. FeCl losses are caused by inefficient condensation.

EXAMPLE 5 The apparatus employed is of the type shown in FIG. 4. 467 g of commercial FeCl described in Example 2 is placed in the lower section of the reactor. A blend of 200 g of the titaniferous sand ore described in Example 1, and 14.0 g of the petroleum coke of Example 2 is placed in the upper section of the reactor.

The ore/carbon blend is fluidized by a stream of argon gas flowing at a rate of 1,120 cc/min. The fluidized blend is heated to 1,050C. and held at this temperature for 60 minutes. Concurrently, the FeCl is heated to 500C. Over a period of 60 minutes the heated FeCl is contactedwith a'stream of O flowing at a rate of 263 cc/min, thereby providing a total of 20.7 g 0 The oxidation results in the intermediate formation of about 280 g of FeClwhich contacts the ore/- carbon blend. Simultaneously, the fluidized ore/carbon blend is contacted with a stream of CO flowing at a rate 'of 74 cc/min for 60 minutes, thereby providing a total of 5.1 g CO. Fluidization of the ore/carbon blend is monitored throughout the reaction and no bed sticking occurs.

The gas flows of CO and 0 are then discontinued and the flow of argon is maintained for another 60 min utes. The reactor is allowed to cool, after which the residual bed is removed, ignited in air at 900C. and analyzed. I

The beneficiate weighs 134 g and analyzes 95.2% TiO and 3.4% Fe O It is determined that the beneficiate retains 98.8% of the Ti and 7.2% of the Fe in the unreacted ore. The formation of TiCl is found to be negligible.

EXAMPLE 6 The apparatus employed is of the type shown in FIG. 4. The composition of the ore/carbon blend is chosen to simulate the bed composition attained in a continuous beneficiation process. 565 g of the FeCl ofExample 2 is placed in the lower section of the reactor. A blend of g of a titaniferous rock ore (analyzing 32.9% total Fe, 29.0% Fe, 44.4% TiQ and the balance consisting primarily of SiO A1 0 and MgO) ground to mesh size 60+1 60, 100 g of a beneficiate of the same ore (analyzing 7.8% Fe O 76.0% TiO and the balance consisting primarily of SiO A1 0 and MgO) of mesh size 60+l60, and9.2 g of the petroleum coke described in Example The ore/carbon blend is fluidized by a stream of argon gas flowing at a rate of 1,120 cc/min. The fluidized blend is heated to 1,050C. and held at this temperature for minutes. Concurrently, the FeCl is heated to 500C. Over a period of 60 minutes, the heated FeC1 is contacted with a stream of O flowing at a rate of 227 cc/min, thereby providing a total of 17.8 g 0 The oxidation results in the formation of about 241 g of FeCl;;, which contacts the ore/carbon blend. Simultaneously, the fluidized ore/carbon blend is contacted with a stream of CO flowing at a rate of 74 cc/min for 60 minutes, thereby providing a total of 5.1 g'CO. Fluidization of the ore/carbon blend is monitored throughout the reaction and no bed sticking occurs.

The gas flows of CO and 0 are then discontinued and the flow of argon is maintained for another 60 minutes. The reactor is allowed to cool, after which the residual bed is removed, ignited in air at 950C. and analyzed.

The beneficiate so obtained weighs 147 g and analyzes 82.6% TiO and 3.2% Fe O It is calculated that the beneficiate retains essentially all the Ti and 8.6% of the Fe in the starting materials.

The reacted bed of FeCl in the upper reactor section is found to contain unreacted FeCl and by-product Fe O The Fe O is freed from unreacted FeCl by waterleaching, is dried Ill air and is analyzed. It con- 1 1 tains anamount of iron essentially equivalent to the iron content of the starting materials.

The amount of Fe in the FeCl which condenses in the receptacle of FlG. 3 equals 91.9% of the amount of Fe in the FeClconsumed by oxidation in the upper reaction section. FeCl losses are caused'by inefficient condensation.

What is claimed is:

1. Cyclic process for selectively chlorinating the iron constituent of titaniferous material comprising passing an oxidizing agent to a first reaction zone, said first reaction zone containing ferrous chloride, thereby oxidizing the ferrous chloride to ferric chloride, the temperature in said first reaction zone being maintained above the boiling point of ferric chloride, passing said ferric chloride to a second reaction zone, said second reaction zone containing said titaniferous material and a reductant, said reductant being selected from at least one of the group consisting of solid carbonaceous material and gaseous carbon monoxide, the amount of carbon in said solid carbonaceous material being greater than the stoichiometric amount for conversion of the oxygen bound to said iron constituent to carbon dioxide and less than or about equal to the stoichiometric amount for conversion of said oxygen to carbon monoxide, the amount of said gaseous carbon monoxide being at least sufficient to convert the balance of said oxygen to carbon dioxide, the temperature in said second reaction zone being at least 950C, thereby chlorinating the iron constituent in said titaniferous material to form ferrous chloride, and recycling ferrous chloride to said 5. Process according to claim 1 wherein the reductant is carbon monoxide.

6. Process according to claim 1 wherein the reductant is carbon and carbon monoxide.

7. Process according to claim 1 wherein the reaction is carried out to chlorinate at least about percent by weight of the iron content of the titaniferous material.

8. Process according to claim 1 wherein the titaniferous material has been prereduced prior to contact with the FeCl;.,.

9. Process according to claim 1 wherein said oxidizing agent is a gaseous mixture containing at least 20 percent molecular oxygen.

10. Process according to claim 1 wherein the said oxidizing agent consists essentially of O 11. Process for selectively chlorinating the iron constituent of a titaniferous material without an appreciable net yield of titanium chloride from the titanium constituent of said material by intimately contacting said material with FeCl at an elevated temperature of at least 950C. and in the presence of a reductant, said reductant being selected from at least one of the group consisting of solid carbonaceous material and gaseous carbon monoxide, the amount of carbon in said solid carbonaceous material being greater than the stoichiometric amount for conversion of the oxygen bound to said iron constituent to carbon dioxide and less than or about equal to the stoichiometric amount for conversion of said oxygen to carbon monoxide, the amount of said gaseous carbon monoxide being at least sufficient to convert the balance of said oxygen to carbon dioxide.

12. Process according to claim 11 wherein the FeCl is produced by the reaction of FeCl; with an oxidizing agent selected from the group consisting of gaseous chlorine and gas containing at least 20 percent molecular oxygen.

13. Process according to claim 12 wherein the oxidizing agent consists essentially of C1 14. Process according to claim 12 wherein the oxidizing agent consists essentially of O 

1. CYCLIC PROCESS FOR SELECTIVELY CHLORINATING THE IRON CONSTITUENT OF TITANIFEROUS MATERIAL COMPRISING PASSING AN OXIDIZING AGENT TO A FIRST REACTION ZONE, SAID FIRST REACTION ZONE CONTAINING FERROUS CHLORIDE, THEREBY OXIDIZING THE FERROUS CHLORIDE TO FERRIC CHLORIDE, THE TEMPERATURE IN SAID FIRST REACTION ZONE BEING MAINTAINED ABOVE THE BOILING POINT OF FERRIC CHLORIDE, PASSING SAID FERRIC CHLORIDE TO A SECOND REACTION ZONE, SAID SECOND REACTION ZONE CONTAINING SAID TITANIFEROUS MATERIAL AND A REDUCTANT, SAID REDUCTANT BEING SELECTED FROM AT LEAST ONE OF THE GROUP CONSISTING OF SOLID CARBONACEOUS MATERIAL AND GASEOUS CARBON MONOXIDE, THE AMOUNT OF CARBON IN SAID SOLID CARBONACEOUS MATERIAL BEING GREATER THAN THE STOICHIOMETRIC AMOUNT FOR CONVERSION OF THE OXYGEN BOUND TO SAID IRON CONSTITUENT TO CARBON DIOXIDE AND LESS THAN OR ABOUT EQUAL TO THE STOICHIOMETRIC AMOUNT FOR CONVERSION OF SAID OXYGEN TO CARBON MONOXIDE, THE AMOUNT OF SAID GASEOUS CARBON MONOXIDE BEING AT LEAST SUFFICIENT TO CONVERT THE BALANCE OF SAID OXYGEN TO CARBON DIOXIDE, THE TEMPERATURE IN SAID SECOND REACTION ZONE BEING AT LEAST 950*C, THEREBY CHLORINATING THE IRON CONSTITUENT IN SAID TITANIFEROUS MATERIAL TO FORM FERROUS CHLORIDE, AND RECYCLING FERROUS CHLORIDE TO SAID FIRST REACTION ZONE.
 2. Process according to claim 1 wherein the titaniferous material contains in excess of about 10% by weight each of titanium and of iron.
 3. Process according to claim 1 wherein the titaniferous material is an oxidic ore containing about 20 to 50 percent by weight titanium.
 4. Process according to claim 1 wherein the reductant is carbon.
 5. Process according to claim 1 wherein the reductant is carbon monoxide.
 6. Process according to claim 1 wherein the reductant is carbon and carbon monoxide.
 7. Process according to claim 1 wherein the reaction is carried out to chlorinate at least about 75 percent by weight of the iron content of the titaniferous material.
 8. Process according to claim 1 wherein the titaniferous material has been prereduced prior to contact with the FeCl3.
 9. Process according to claim 1 wherein said oxidizing agent is a gaseous mixture containing at least 20 percent molecular oxygen.
 10. Process according to claim 1 wherein the said oxidizing agent consists essentially of O2.
 11. Process for selectively chlorinating the iron constituent of a titaniferous material without an appreciable net yield of titanium chloride from the titanium constituent of said material by intimately contacting said material with FeCl3 at an elevated temperature of at least 950*C. and in the presence of a reductant, said reductant being selected from at least one of the group consisting of solid carbonaceous material and gaseous carbon monoxide, the amount of carbon in said solid carbonaceous material being greater than the stoichiometric amount for conversion of the oxygen bound to said iron constituent to carbon dioxide and less than or about equal to the stoichiometric amount for conversion of said oxygen to carbon monoxide, the amount of said gaseous carbon monoxide being at least sufficient to convert the balance of said oxygen to carbon dioxide.
 12. Process according to claim 11 wherein the FeCl3 is produced by the reaction of FeCl2 with an oxidizing agent selected from the group consisting of gaseous chlorine and gas containing at least 20 percent molecular oxygen.
 13. Process according to claim 12 wherein the oxidizing agent consists essentially of Cl2.
 14. Process according to claim 12 wherein the oxidizing agent consists essentially of O2. 